Organohydrogensilicon compounds

ABSTRACT

Organohydrogensilicon compounds containing at least one silicon-bonded hydrogen atom per molecule and at least one cyclosiloxane.

The invention relates to organohydrogensilicon compounds containing atleast one silicon-bonded hydrogen atom per molecule and at least onecyclosiloxane.

Hydrosilylation is a well known method for coupling different materials.Generally for hydrosilylation one needs a material having at least onealiphatic unsaturation and a material having at least one SiH group.Depending on the average number of SiH to aliphatic unsaturation presentin the molecules, this coupling may include chain extension orcrosslinking/curing. Silicone compositions which cure by hydrosilylationare useful in a wide variety of applications to produce coatings,elastomers, adhesives, foams or fluids. The basic constituents ofsilicone compositions which cure by hydrosilylation include analkenylated polydiorganosiloxane, typically a linear polymer withterminal alkenyl groups, a polyorganohydrogensiloxane crosslinkingagent, designed to cross-link the alkenylated polydiorganosiloxane and acatalyst, to catalyze the aforementioned cross-linking reaction.

Improvements in the performance of compositions which cure byhydrosilylation are continuously being sought with respect to, forexample, ease of cure, i.e. the decrease in cure times at relatively lowtemperatures, extended working time of a formulated bath, i.e. longerthin film and bulk bath life, anchorage of coatings to a substraterelease performance and particularly for high catalyst coatings such asrelease coatings, maintenance of exceptional performance in theaforementioned areas with decreased catalyst level and thereforedecreased cost.

A critical parameter in achieving the optimal performance forcompositions which cure by hydrosilylation is the structure of thepolyorganohydrogensiloxane cross-linking agent. Standard structureswhich are commonly used include trimethylsilyl endcappedmethylhydrogensiloxane polymers, trimethylsilyl endcappedmethylhydrogen, dimethyl siloxane copolymers and hydrogendimethylsilylendcapped dimethylsiloxane polymers. Variations to include branching orresinous structures are also known.

The instant invention teaches novel organohydrogensilicon compoundscontaining at least one silicon-bonded hydrogen atom per molecule and atleast one cyclosiloxane which are useful in hydrosilylation reactions.

The present invention relates to organohydrogensilicon compoundscontaining at least one silicon-bonded hydrogen atom per molecule and atleast one cyclosiloxane.

The present invention relates to organohydrogensilicon compoundscontaining at least one silicon-bonded hydrogen atom per moleculedescribed by formula (I)

where each R is independently selected from a hydrogen atom and amonovalent hydrocarbon group comprising 1 to 20 carbon atoms which isfree from aliphatic unsaturation, a is an integer from 1 to 18, b is aninteger from 1 to 19, a+b is an integer from 3 to 20, each X is anindependently selected functional group selected from a halogen atom, anether group, an alkoxy group, an alkoxyether group, an acyl group, anepoxy group, an amino group, or a silyl group, or a -Z-R⁴ group, whereeach Z is independently selected from an oxygen and a divalenthydrocarbon group comprising 2 to 20 carbon atoms, each R⁴ group isindependently selected from —BR_(u)Y_(2-u), —SiR_(v)Y_(3-v), or a groupdescribed by formula (II):(Y_(3-n)R_(n)SiO_(1/2))_(c)(Y_(2-o)R_(o)SiO_(2/2))_(d)(Y_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)Y_(1-q))_(g)(CR_(r)Y_(2-r))_(h)(O(CR_(s)Y_(2-s))_(i)(CR_(t)Y_(3-t))_(j)where B refers to boron, each R is as described above, the sum ofc+d+e+f+g+h+i+j is at least 2, n is an integer from 0 to 3, o is aninteger from 0 to 2, p is an integer from 0 to 1, q is an integer from 0to 1, r is an integer from 0 to 2, s is an integer from 0 to 2, t is aninteger from 0 to 3, u is an integer from 0 to 2, v is an integer from 0to 3, each Y is an independently selected functional group selected froma halogen atom, an ether group, an alkoxy group, an alkoxyether group,an acyl group, an epoxy group, an amino group, or a silyl group, or aZ-G group, where Z is as described above, each G is a cyclosiloxanedescribed by formula (III):

where R and X are as described above, k is an integer from 0 to 18, m isan integer from 0 to 18, k+m is an integer from 2 to 20, provided informula (II) that one of the Y groups is replaced by the Z group bondingthe R⁴ group to the cyclosiloxane of formula (I), and provided further(a) at least one X group of Formula (I) is a -Z-R⁴ group, (b) if Z is adivalent hydrocarbon group, a=1, c=2, e+f+g+h+i+j=0 and d>0, then atleast one d unit (ie. Y_(2-o)R_(o)SiO_(2/2)) contain a -Z-G group or thec units (ie. Y_(3-n)R_(n)SiO_(1/2)) have no -Z-G group or at least two-Z-G groups, (c) if Z is a divalent hydrocarbon group, a=1, c=2 andd+e+f+g+b+i+j=0, then the c units (ie. Y_(3-n)R_(n)SiO_(1/2)) have no-Z-G group or at least two -Z-G groups, and (d) if g+h+i+j>0 thenc+d+e+f>0.

The present invention also relates to organohydrogensilicon compoundscontaining at least one silicon-bonded hydrogen atom per moleculedescribed by formula (I)

where each R is independently selected from a hydrogen atom and amonovalent hydrocarbon group comprising 1 to 20 carbon atoms which isfree from aliphatic unsaturation, a is an integer from 1 to 18, b is aninteger from 2 to 19, a+b is an integer from 3 to 20, each X is anindependently selected functional group selected from a halogen atom, anether group, an alkoxy group, an alkoxyether group, an acyl group, anepoxy group, an amino group, or a silyl group, or a -Z-R⁴ group, whereeach Z is independently selected from an oxygen and a divalenthydrocarbon group comprising 2 to 20 carbon atoms, each R⁴ group isindependently selected from —BR_(u)Y_(2-u), —SiR_(v)Y_(3-v), or a groupdescribed by formula (II):(Y_(3-n)R_(n)SiO_(1/2))_(c)(Y_(2-o)R_(o)SiO_(2/2))_(d)(Y_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)Y_(1-q))_(g)(CR_(r)Y_(2-r))_(h)(O(CR_(s)Y_(2-s))_(i)(CR_(t)Y_(3-t))_(j)where B refers to boron, each R is as described above, the sum ofc+d+e+f+g+h+i+j is at least 2, n is an integer from 0 to 3, o is aninteger from 0 to 2, p is an integer from 0 to 1, q is an integer from 0to 1, r is an integer from 0 to 2, s is an integer from 0 to 2, t is aninteger from 0 to 3, u is an integer from 0 to 2, v is an integer from 0to 3, each Y is an independently selected functional group selected froma halogen atom, an ether group, an alkoxy group, an alkoxyether group,an acyl group, an epoxy group, an amino group, or a silyl group, or aZ-G group, where Z is as described above, each G is a cyclosiloxanedescribed by formula (III):

where R and X are as described above, k is an integer from 0 to 18, m isan integer from 0 to 18, k+m is an integer from 2 to 20, provided informula (II) that one of the Y groups is replaced by the Z group bondingthe R⁴ group to the cyclosiloxane of formula (I), and provided further(a) at least one X group of Formula (I) is a -Z-R⁴ group, (b) if Z is adivalent hydrocarbon group, a=1, c=2, e+f+g+h+i+j=0 and d>0, then atleast one d unit (ie. Y_(2-o)R_(o)SiO_(2/2)) contain a -Z-G group or thec units (ie. Y_(3-n)R_(n)SiO_(1/2)) have no -Z-G group or at least two-Z-G groups, (c) if Z is a divalent hydrocarbon group, a=1, c=2 andd+e+f+g+h+i+j=0, then the c units (ie. Y_(3-n)R_(n)SiO_(1/2)) have no-Z-G group or at least two -Z-G groups, and (d) if g+h+i+j>0 thenc+d+e+f>0.

As used herein, the term “aliphatic unsaturation” refers to acarbon-carbon multiple bond.

In formulas (I), (II), and (III), each R group is independently selectedfrom a hydrogen atom and a monovalent hydrocarbon group comprising 1 to20 carbon atoms free from aliphatic unsaturation. Each monovalenthydrocarbon group of R can be linear, branched or cyclic. Eachmonovalent hydrocarbon group of R can be unsubstituted or substitutedwith halogen atoms. The monovalent hydrocarbon group of R can beexemplified by alkyl groups such as methyl, ethyl, propyl, butyl, hexyl,octyl, 3,3,3-trifluoropropyl, nonafluorobutylethyl, chloromethyl, anddecyl, cycloaliphatic groups such as cyclohexyl, aryl groups such asphenyl, tolyl, and xylyl, chorophenyl, and aralkyl groups such asbenzyl, styryl and alpha-methylstyryl. It is preferred that each R groupis independently selected from hydrogen atoms, alkyl groups comprising 1to 8 carbon atoms, or aryl groups comprising 6 to 9 carbon atoms. It ismost preferrred that each R group is independently selected fromhydrogen, methyl, alpha-methylstyryl, 3,3,3-trifluoropropyl andnonafluorobutylethyl. Each R can be identical or different, as desired.

In formulas (I) and (III), each X is an independently selectedfunctional group selected from a halogen atom, an ether group, an alkoxygroup, an alkoxyether group, an acyl group, an epoxy group, an aminogroup, or a silyl group, or a -Z-R⁴ group.

The functional groups represented by X are selected from halogen atoms,ether groups, alkoxy groups, alkoxyether groups, acyl groups, groups,epoxy groups, amino groups, or silyl groups. Examples of usefulfunctional groups include chloro, fluoro, bromo, methoxy, ethoxy,isopropoxy, and oxybutylvinyl ether. Other useful functional groups arederived by hydrosilylation of the alkenyl group from methylvinylether,methylvinylketone, vinylacetate, vinylbenzoate, vinylacrylate,vinylstearate, vinyldecanoate, vinylmethacrylate,vinylcyclohexylepoxide, allylglycidylether,vinylcyclohexylepoxidetrimethoxysilane, trimethylvinylsilane,triethylvinylsilane, vinyltrimethoxysilane, vinyltriacetoxysilane,vinylpyridine, phenylvinylether, phenylvinylketone, and allyl aldehydewith an SiH from the siloxane precursor to formulas (I) or (III), wherethe term siloxane precursor includes the siloxane material used to makethe initial formula (I) or (III) material and any initial formula (I)material which can then be further reacted.

When X is a functional group, it is preferred that each X isindependently selected from chloro, methoxy, isopropoxy, and groupsderived by hydrosilylation of the alkenyl group from hydroxybutylvinylether, vinylcyclohexylepoxide, and allylglycidylether with an SiH fromthe siloxane precursor to formulas (I) or (III), where the term siloxaneprecursor includes the siloxane material used to make the initialformula (I) or (III) material and any initial formula (I) material whichcan then be further reacted.

Each X of formulas (I) and (III) may also comprise a Z-R⁴ group. It ispreferred that X is a Z-R⁴ group. It is more preferred that X includesboth -Z-R⁴ groups and functional groups derived by hydrosilylation ofallylglycidyl ether (ie. propylglycidyl ether) orvinylcyclohexylepoxide.

Each Z is independently selected from oxygen and divalent hydrocarbongroups comprising 2 to 20 carbon atoms. Examples of the divalenthydrocarbon group comprising 2 to 20 carbon atoms represented by Zinclude alkylene radicals such as methylene, ethylene, methylmethylene,propylene, isopropylene, butylene, pentylene, hexylene, andoctadecylene; alkenylene radicals such as vinylene, allylene,butenylene, and hexenylene, arylene radicals such as phenylene andxylylene; aralkylene radicals as benzylene; and alkarylene radicals suchas tolylene. Preferably, Z is a divalent hydrocarbon group comprising 2to 18 carbon atoms. It is more preferred for Z to be an alkylene group,with an alkylene group comprising 2 to 8 carbon atoms being mostpreferred.

Each R⁴ group is selected from —BR_(u)Y_(2-u), —SiR_(v)Y_(3-v), or agroup described by formula (II)(Y_(3-n)R_(n)SiO_(1/2))_(c)(Y_(2-o)R_(o)SiO_(2/2))_(d)(Y_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)Y_(1-q))_(g)(CR_(r)Y_(2-r))_(h)(O(CR_(s)Y_(2-s))_(i)(CR_(t)Y_(3-t))_(j),where R, Y, c, d, e, f, g, h, i, j, n, o, p, q, r, s, t, u, v are asdescribed above, provided in formula (II) that one of the Y groups isreplaced by the Z group bonding the R⁴ group to the cyclosiloxane offormula (I).

In formula (I), a is an integer from 1 to 18, b is an integer from 1 to19, preferably from 2 to 19, and a+b is an integer from 3 to 20.

In formula (II), the sum of c+d+e+f+g+h+i+j is at least 2, preferablyfrom 2 to 5300, more preferably from 2 to 1000. Preferably, subscript cis an integer from 0 to 50, with 2 to 15 being more preferred, and 2 to10 being most preferred. Preferably, subscript d is an integer from 0 to5000, with 0 to 1000 being more preferred, and 1 to 50 being mostpreferred. Preferably, subscript e is an integer from 0 to 48, with 0 to13 being more preferred, and 0 to 8 being most preferred. Preferably,subscript f is an integer from 0 to 24, with 0 to 6 being morepreferred, and 0 to 4 being most preferred. Preferably, subscript g isan integer from 0 to 50, with 0 to 20 being more preferred, and 0 to 10being most preferred. Preferably, subscript h is an integer from 0 to50, with 0 to 20 being more preferred, and 0 to 10 being most preferred.Preferably, subscript i is an integer from 0 to 50, with 0 to 20 beingmore preferred, and 0 to 10 being most preferred. Preferably, subscriptj is an integer from 0 to 50, with 0 to 15 being more preferred, and 0to 10 being most preferred.

In formula (II), n is an integer from 0 to 3, preferably from 2 to 3; ois an integer from 0 to 2, preferably from 1 to 2; p is an integer from0 to 1, preferably 1; q is an integer from 0 to 1, preferably 1; r is aninteger from 0 to 2, preferably from 1 to 2; s is an integer from 0 to2, preferably from 1 to 2; and t is an integer from 0 to 3, preferablyfrom 2 to 3. Notwithstanding the above, since the R⁴ group as describedby formula (II) is connected to the cyclosiloxane described by formula(I) via a Z group, one of the Y groups present in the R⁴ group describedby formula (II) will be replaced by a Z group.

In addition to a group described by formula (II) each R⁴ group isindependently selected from —BR_(u)Y_(2-u), and —SiR_(v)Y_(3-v) where Brefers to boron, u is an integer from 0 to 2, preferably from 1 to 2 andv is an integer from 0 to 3, preferably from 2 to 3. Examples of theseR⁴ groups are derived from borane or silanes, such as for example,trivinylborane, diallyldimethylsi lane, divinyldimethylsilane andvinyltrimethylsilane.

Each Y of R⁴ is an independently selected functional group selected froma halogen atom, an ether group, an alkoxy group, an alkoxyether group,an acyl group, an epoxy group, an amino group, or a silyl group, or a-Z-G group. The functional groups are exemplified as described above forX. The Z group is also as described above.

Each G is a cyclosiloxane described by formula (III):

where R and X are as described above, k is an integer from 0 to 18, m isan integer from 0 to 18, and k+m is an integer from 2 to 20.

In formula (III), each k is an integer from 0 to 18, preferably from 1to 3.

In formula (III), each m is an integer from 0 to 18, preferably from 1to 10, most preferably from 2 to 4.

The sum of k+m is an integer from 2 to 20, preferably from 2 to 6, mostpreferably from 2 to 5.

The Y group of formula (II) is preferably a -Z-G group. Although it isnot required for there to be any -Z-G groups in theorganohydrogensilicon compound of the present invention, it is preferredthat on average the organohydrogensilicon compound contain at least1-Z-G group with at least 2-Z-G groups being more preferred.

The R⁴ group described by formula (II) can be linear, cyclic, branchedor resinous. The R⁴ group described by formula (II) can be a siloxanematerial where the polymer chain units contain only siloxane units, orit can be a mixture of siloxane units with hydrocarbon units, oroxyhydrocarbon units, where oxyhydrocarbon refers to a hydrocarbon groupwhich also includes at least one oxygen atom. It is preferred that theR⁴ group is a siloxane material, and more preferred that R⁴ is a linearsiloxane material.

Examples of preferred R⁴ groups described by formula (II) useful in theinvention include —R₂SiO(R₂SiO)_(d)SiR₂-Z-G, —R₂SiOSiR₃, —R₂SiOSiR₂—Y,—RSi(OSiR₃)₂, where d is an integer from 1 to 50 and Z, G, and R are asdescribed above. More preferred R⁴ groups are as described above when Ris methyl, and d is an average of 8.

With respect to the organohydrogensilicon compounds of the presentinvention it is preferred that (a) at least one X group of Formula (I)is a -Z-R⁴ group (b) if Z is a divalent hydrocarbon group, a=1, c=2,e+f+g+h+i+j=0 and d>0, then at least one d unit (ie.Y_(2-o)R_(o)SiO_(2/2)) contain a -Z-G group or the c units (ie.Y_(3-n)R_(n)SiO_(1/2)) have no -Z-G group or at least two -Z-G groups,(c) if Z is a divalent hydrocarbon group, a=1, c=2 and d+e+f+g+h+i+j=0,then the c units (ie. Y_(3-n)R_(n)SiO_(1/2)) have no -Z-G group or atleast two -Z-G groups, and (d) if g+h+i+j>0 then c+d+e+f>0.

It is also preferred that the organohydrogensilicon compounds of thepresent invention have a viscosity from 5 to 50,000 mPa·s, morepreferred from 10 to 10,000 mPa·s and most preferred from 25 to 2,000mPa·s.

The organohydrogensilicon compounds of the present invention contain atleast one silicon-bonded hydrogen atom per molecule. Preferably, theorganohydrogensilicon compounds contain at least 2 silicon-bondedhydrogen atoms per molecule. It is most preferred that theorganohydrogensilicon compounds contain at least 3 silicon-bondedhydrogen atoms per molecule.

Examples of the types of organohydrogensilicon compounds included in thescope of the present invention are as follows where Me is methyl, d(which equals d₁+d₂) is as described above, and x can range from 1 to100; preferably 1 to 20.

Other examples include the compounds described above where certain ofthe SiH bonds are replaced by hydrocarbon, oxyhydrocarbon or functionalgroups. When these SiH bonds are replaced with the above-describedgroups, it is preferred that 5 to 70% of the SiH bonds are replaced withsuch other groups, more preferably 5 to 50%, most preferably 10 to 30%

Examples of the hydrocarbon, oxyhydrocarbon and functional groupsdescribed above include the types of groups described later in thisspecification for group A. Preferred groups include functional groupsderived by hydrosilylation of allylglycidyl ether (ie. propylglycidylether) or vinylcyclohexylepoxide, alkyl groups such as 1-hexyl, 1-octyl,and ethylcyclohexene and alkenyl groups such as 5-hexenyl. It is mostpreferred that the SiH bonds are replaced by functional groups derivedby hydrosilylation of allylglycidyl ether.

The most preferred organohydrogensilicon compounds described by formula(I) include the compound described below where Me is methyl, d is anaverage of 8 and x is an integer from 1 to 15 and the compound describedbelow when 10 to 30% of the SiH bonds are replaced by functional groupsderived by hydrosilylation of allylglycidyl ether.

The compounds described by Formula I can be made in a straightforwardmanner, for example via a platinum catalyzed coupling of methylhydrogencyclosiloxanes with a reactant containing aliphatic unsaturation,hydroxy functionalities or a mixture of both. The desired product is afunction not only of the reactants but also of the reactionstoichiometry. The reaction can be conducted by premixing the reactantsfollowed by catalysis or by using one of the reactants as a controllingreagent. Once an initial organohydrogensilicon compound is prepared,subsequent hydrosilylations or condensations may also be done to replaceor convert some of the remaining SiH bonds to other types of groups.After the desired organohydrogensilicon compound is made it is preferredto deactivate the catalyst using an inhibitor.

Generally, the ratio of SiH to aliphatic unsaturation or SiH to hydroxyfunctionality useful to prepare the organohydrogensilicon compounds ofthe present invention is at least 2.5:1. It is preferred that a ratio ofSiH to aliphatic unsaturation ratio or SiH to hydroxy functionality of20:1 to 2.5:1 be used with a ratio of 4:1 to 3:1 being most preferred.Notwithstanding the above, if organohydrogensilicon compounds describedby formula (I) which are prepared using the above ratios are thenfurther hydrosilylated or condensed, for example to convert or replacesome of the remaining SiH groups and form other organohydrogensiliconcompounds described by formula (I), the ratio of SiH to aliphaticunsaturation or SiH to hydroxy functionality to be used for thesesubsequent reactions need not follow the above recommendations butrather is limited only by the amount of SiH which is desired on suchfinal organohydrogensilicon compound.

In one preferred embodiment, the organohydrogensilicon compounds havingat least one silicon-bonded hydrogen are prepared by (1) mixing (A) atleast one organohydrogen cyclosiloxane comprising at least 2 SiH bondsper molecule and having the formula

with (B) at least one compound comprising at least one aliphaticunsaturation or at least one hydroxy group per molecule described byBR_(u)A_(3-u), SiR_(v)A_(4-v), or a group described by formula(A_(3-n)R_(n)SiO_(1/2))_(c)(A_(2-o)R_(o)SiO_(2/2))_(d)(A_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)A_(1-q))_(g)(CR_(r)A_(2-r))_(h)(O(CR_(s)A_(2-s))_(i)(CR_(t)A_(3-t))_(j)so that ratio of SiH bonds in component (A) to the aliphaticunsaturation or hydroxy group of component (B) is at least 2.5:1; (2)effecting a reaction between components (A) and (B) in the presence of(C) a catalyst to form a reaction mixture comprisingorganohydrogensilicon compounds having at least one SiH bond permolecule described by formula (I) above; (3) optionally, adding aninhibitor to the reaction mixture; and (4) optionally, isolating theorganohydrogensilicon compounds; where B is boron, X, R, a, b, c, d, e,f, g, h, i, j, n, o, p, q, r, s, t, u, v are as defined above, and eachA is independently selected from a hydroxy group, a monovalenthydrocarbon group comprising 2 to about 20 carbon atoms having at leastone aliphatic unsaturation, a monovalent oxyhydrocarbon group comprising2 to about 20 carbon atoms having at least one aliphatic unsaturation,or a functional group selected from a halogen atom, an ether group, analkoxy group, an alkoxyether group, an acyl group, an epoxy group, anamino group, or a silyl group, provided at least one A group has analiphatic unsaturation or a hydroxy group.

In another preferred embodiment, the organohydrogensilicon compoundshaving at least one silicon-bonded hydrogen are prepared by (1′) mixing(A) at least one organohydrogen cyclosiloxane comprising at least 2 SiHbonds per molecule and having the formula

with (C) a catalyst to form a SiH premix; (2′) effecting a reaction byadding to the SiH premix (B) at least one compound comprising at leastone aliphatic unsaturation or at least one hydroxy group per moleculedescribed by BR_(u)A_(3-u), SiR_(v)A_(4-v), or a group described byformula(A_(3-n)R_(n)SiO_(1/2))_(c)(A_(2-o)R_(o)SiO_(2/2))_(d)(A_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)A_(1-q))_(g)(CR_(r)A_(2-r))_(h)(O(CR_(s)A_(2-s))_(i)(CR_(t)A_(3-t))_(j)so that ratio of SiH bonds in component (A) to the aliphaticunsaturation or hydroxy group of component (B) is at least 2.5 to form areaction mixture comprising organohydrogensilicon compounds having atleast one SiH bond per molecule described by formula (I) above; (3′)optionally, adding an inhibitor to the reaction mixture; and (4′)optionally, isolating the organohydrogensilicon compounds; where B isboron, and A, X, R, a, b, c, d, e, f, g, h, i, j, n, o, p, q, r, s, t,u, and v are as defined above.

In another preferred embodiment, the organohydrogensilicon compoundshaving at least one silicon-bonded hydrogen are prepared by (1″) mixing(B) at least one compound comprising at least one aliphatic unsaturationor at least one hydroxy group per molecule described by BR_(u)A_(3-u),SiR_(v)A_(4-v), or a group described by formula(A_(3-n)R_(n)SiO_(1/2))_(c)(A_(2-o)R_(o)SiO_(2/2))_(d)(A_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)A^(1-q))_(g)(CR_(r)A_(2-r))_(h)(O(CR_(s)A_(2-s))_(i)(CR_(t)A_(3-t))_(j),with (C) a catalyst to form a aliphatic unsaturation premix or hydroxypremix respectively; (2″) effecting a reaction by adding the aliphaticunsaturation premix or hydroxy premix to (A) at least one organohydrogencyclosiloxane comprising at least 2 SiH bonds per molecule and havingthe formula

so that ratio of SiH bonds in component (A) to the aliphaticunsaturation or hydroxy group of component (B) is at least 2.5 to form areaction mixture comprising organohydrogensilicon compounds having atleast one SiH bond per molecule described by formula (I) above; (3″)optionally, adding an inhibitor to the reaction mixture; and (4″)optionally, isolating the organohydrogensilicon compounds; where B isboron, and A, X, R, a, b, c, d, e, f, g, h, i, j, n, o, p, q, r, s, t,u, and v are as defined above.

Each A group may be independently selected from functional groupsselected from a halogen atom, an ether group, an alkoxy group, analkoxyether group, an acyl group, an epoxy group, an amino group, or asilyl group. Examples of such functional groups represented by A are asdescribed above for X.

Each A group may also be independently selected from hydroxy groups,monovalent hydrocarbon groups comprising 2 to 20 carbon atoms having atleast one aliphatic unsaturation and monovalent oxyhydrocarbon groupscomprising 2 to 20 carbon atoms having at least one aliphaticsaturation. The aliphatic unsaturations of A can be found in a pendantposition to the hydrocarbon chain, at the end of the hydrocarbon chain,or both, with the terminal position being preferred. Each monovalenthydrocarbon group and oxyhydrocarbon group of A can be linear, branchedor cyclic and may be unsubstituted or substituted with halogen atoms.Examples of monovalent hydrocarbon groups comprising 2 to 20 carbonatoms having aliphatic unsaturation include alkenyl groups such asvinyl, allyl, 3-butenyl, 4-pentenyl, 5-hexenyl, cyclohexenyl,6-heptenyl, 7-octenyl, 8-nonenyl, 9-decenyl, 10-undecenyl, and dienegroups comprising 4 to 20 carbon atoms such as 4,7-octadienyl,5,8-nonadienyl, 5,9-decadienyl, 6,11-dodecadienyl, 4,8-nonadienyl, and7,13-tetradecadienyl. Examples of monovalent oxyhydrocarbon groupscomprising 2 to 20 carbon atoms include alkenyloxy groups such asoxybutylvinylether and alkynyloxy groups such as propargyloxy orhexynyloxy.

Preferably, each A is independently selected from a monovalenthydrocarbon group comprising 2 to 20 carbon atoms having aliphaticunsaturation, a hydroxy group, or an epoxy group. It is more preferredfor A to be an alkenyl radical, with an alkenyl radical comprising 2 toabout 8 carbon atoms being most preferred for A.

The methods described above for making organohydrogensilicon compoundshaving at least one SiH group per molecule, are examples of somepreferred methods and are not meant to describe all the various methodsof making such materials. Depending on the starting materials used andthe desired organohydrogensilicon compound, the initialorganohydrogensilicon compound formed may be subjected to subsequenthydrosilylations and/or condensations utilizing at least onehydrocarbon, oxyhydrocarbon or functional compound having at least onealiphatic unsaturation or hydroxy group so to form the desiredorganohydrogensilicon compound having at least one SiH group permolecule as described by Formula (I).

The methods described above preferably further comprise step (2a), (2′a)or (2″a) adding at least one hydrocarbon, oxyhydrocarbon or functionalcompound having at least one aliphatic unsaturation or hydroxy group tothe reaction mixture comprising organohydrogensilicon compounds havingat least one SiH bond per molecule formed in step (2), (2′), or (2″)respectively so to form a second reaction mixture comprisingorganohydrogensilicon compounds having at least one SiH bond permolecule where a certain percentage of SiH groups have been converted tohydrocarbon, oxyhydrocarbon or functional groups.

Examples of the hydrocarbon, oxyhydrocarbon and functional compoundshaving at least one aliphatic unsaturation or hydroxy group useful forthese subsequent reactions include compounds which contain the type ofgroups described above for A so long as they also include either aaliphatic unsaturation or hydroxy group. Preferred compounds includefunctional compounds such as allylglycidyl ether andvinylcyclohexylepoxide, alkenes such as 1-hexene, 1-octene, andvinylcyclohexene and dienes such as 1,5-hexadiene.

When these subsequent reactions are utilized it is preferred that 5 to70% of the SiH groups are replaced or converted to hydrocarbon,oxyhydrocarbon or functional groups, more preferably 5 to 50% and mostpreferably 10 to 30%.

The organohydrogensiloxanes of component (A) may be prepared by knownmethods or are commercially available. It is preferred that theorganohydrogen cyclosiloxanes used in the reaction are relatively pureand substantially free from oligomeric linears. The compounds ofcomponent (B) containing at least one aliphatic unsaturation or hydroxygroup may also be prepared by known methods or are commerciallyavailable.

Catalysts typically employed for hydrosilylation and/or condensationreactions are used for the reaction between components (A) and (B). Itis preferred to use platinum group metal-containing catalysts. Byplatinum group it is meant ruthenium, rhodium, palladium, osmium,iridium and platinum and complexes thereof. Platinum groupmetal-containing catalysts useful in preparing theorganohydrogensiloxane are the platinum complexes prepared as describedby Willing, U.S. Pat. No. 3,419,593, and Brown et al, U.S. Pat. No.5,175,325, each of which is hereby incorporated by reference to showsuch complexes and their preparation. Other examples of useful platinumgroup metal-containing catalysts can be found in Lee et al., U.S. Pat.No. 3,989,668; Chang et al., U.S. Pat. No. 5,036,117; Ashby, U.S. Pat.No. 3,159,601; Lamoreaux, U.S. Pat. No. 3,220,972; Chalk et al., U.S.Pat. No. 3,296,291; Modic, U.S. Pat. No. 3,516,946; Karstedt, U.S. Pat.No. 3,814,730; and Chandra et al., U.S. Pat. No. 3,928,629 all of whichare hereby incorporated by reference to show useful platinum groupmetal-containing catalysts and methods for their preparation. Theplatinum-containing catalyst can be platinum metal, platinum metaldeposited on a carrier such as silica gel or powdered charcoal, or acompound or complex of a platinum group metal. Preferredplatinum-containing catalysts include chloroplatinic acid, either inhexahydrate form or anhydrous form, and or a platinum-containingcatalyst which is obtained by a method comprising reactingchloroplatinic acid with an aliphatically unsaturated organosiliconcompound such as divinyltetramethyldisiloxane, or alkene-platinum-silylcomplexes as described in U.S. patent application Ser. No. 10/017,229,filed Dec. 7, 2001, such as (COD)Pt(SiMeCl₂)₂, where COD is1,5-cyclooctadiene and Me is methyl. These alkene-platinum-silylcomplexes may be prepared, for example by mixing 0.015 mole (COD)PtCl₂with 0.045 mole COD and 0.0612 moles HMeSiCl₂.

The appropriate amount of the catalyst will depend upon the particularcatalyst used. The platinum catalyst should be present in an amountsufficient to provide at least 2 parts per million (ppm), preferably 5to 200 ppm of platinum based on total weight percent solids (allnon-solvent ingredients) in the composition. It is highly preferred thatthe platinum is present in an amount sufficient to provide 5 to 150weight ppm of platinum on the same basis. The catalyst may be added as asingle species or as a mixture of two or more different species. Addingthe catalyst as a single species is preferred.

Components (A)-(C), and any optional components can be mixed togetherusing any suitable mixing means, such as a spatula, a drum roller, amechanical stirrer, a three roll mill, a sigma blade mixer, a breaddough mixer, and a two roll mill.

The temperature of the reaction is not strictly specified, but generallyfalls within the range of about 20° to 150° C. The length of reactiontime is also not critical, and is generally determined by the additionrate of controlling reagent.

Optionally, the reaction can be run using common solvents such astoluene, xylene, methylisobutylketone, and heptane.

The manner in which the reaction is conducted is important. Since it isdesired to react aliphatically unsaturated groups or hydroxy groupsrandomly with as many SiH containing molecules as possible, the reactionmay be conducted by premixing component (A) and (B) and then catalyzingthe premix; by pre-catalyzing component (A) followed by controlledintroduction of component (B), by precatalyzing component (B) and thenadd this premix to component (A), or by something in between these threeextremes.

After the organohydrogensilicon compound having at least one SiH bond isprepared, an additional preferred step is to deactivate the catalystusing an inhibitor. As used herein, the term “inhibitor” means amaterial that retards activity of a catalyst at room temperature butdoes not interfere with the properties of the catalyst at elevatedtemperatures. It is preferred to use an inhibitor which will not impactdownstream curability. These inhibitors are well known in the art andinclude maleates, fumarates, acetylenic alcohols, eneynes and silylatedacetylenic alcohols. Examples of suitable inhibitors includeethylenically or aromatically unsaturated amides, acetylenic compounds,silylated acetylenic compounds, ethylenically unsaturated isocyanates,olefinic siloxanes, unsaturated hydrocarbon monoesters and diesters,conjugated ene-ynes, hydroperoxides, nitriles, and diaziridines.

Preferred inhibitors include acetylenic alcohols exemplified byl-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol,2-ethynyl-isopropanol, 2-ethynyl-butane-2-ol, and3,5-dimethyl-1-hexyn-3-ol, silylated acetylenic alcohols exemplified bytrimethyl(3,5-dimethyl-1-hexyn-3-oxy)silane,dimethyl-bis-(3-methyl-1-butyn-oxy)silane,methylvinylbis(3-methyl-1-butyn-3-oxy)silane, and((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, unsaturated hydrocarbonmonoesters and diesters exemplified by diallyl maleate, dimethylmaleate, diethyl fumarate, diallyl fumarate, andbis-2-methoxy-1-methylethylmaleate, mono-octylmaleate,mono-isooctylmaleate, mono-allyl maleate, mono-methyl maleate,mono-ethyl ftimarate, mono-allyl fumarate, and2-methoxy-1-methylethylmaleate; conjugated ene-ynes exemplified by2-isobutyl-1-butene-3-yne, 3,5-dimethyl-3-hexene-1-yne,3-methyl-3-pentene-1-yne, 3-methyl-3-hexene-1-yne, 1-ethynylcyclohexene,3-ethyl-3-butene-1-yne, and 3-phenyl-3-butene-1-yne, vinylcyclosiloxanessuch as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and amixture of a conjugated ene-yne as described above and avinylcyclosiloxane as described above.

Most preferred inhibitors are diallyl maleate,bis-2-methoxy-1-methylethylmaleate, 1-ethynyl-1-cyclohexanol, and3,5-dimethyl-1-hexyn-3-ol.

The optimal level of inhibitor used for deactivation will vary for eachinhibitor. Generally, a level of 0.2-1 wt % based on total weightpercent solids (all non-solvent ingredients) in the composition isdesired.

Once the platinum catalyst has been deactivated, routine volatilestripping procedures can be used to remove unreacted polyorganohydrogencyclic siloxanes and any solvent that may have been used.

The organohydrogensilicon compounds comprising at least onesilicon-bonded hydrogen described by Formula (I) are useful for avariety of applications involving coupling reactions, in particularhydrosilylation reactions. Some of the uses of these organohydrogensilicon compounds include use as a crosslinking agent in the preparationof coatings such as paper or film release coatings, textile coatings orprotective electronic coatings; use as a crosslinker for the curing ofliquid silicone rubber (LSR) formulations and use as an SiH intermediatefor the preparation of functional silicone additives and fluids.

The following examples are disclosed to further teach, but not limit,the invention, which is properly delineated by the appended claims.

Test Methods

Gas Chromatography (GC)—GC data was collected on an HP5890A equippedwith an FID and a J&W Scientific 30 m by 0.25 mm i.d. DB-1 column with0.25 micron film thickness.

Gel Permeation Chromatography (GPC)—GPC data was collected using aWaters 515 pump, a Water 717 autosampler and a Waters 2410 differentialrefractometer. The separation was made with two (300 mm×7.5 mm) PolymerLaboratories Plgel 5 um Mixed-C columns, preceded by a Plgel 5 um guardcolumn. HPLC grade toluene eluent was used at 1.0 mL/min flowrate andcolumns and detector were heated to 45° C. An injection volume of 50 uLwas used and the sample prefiltered through a 0.45 um PTFE syringefilter. Molecular weight averages were determined relative to acalibration curve (4^(th) order) created using polydimethylsiloxane(PDMS) standards covering the molecular weight range of 1300-850,000.

Silicon 29 Nuclear Magnetic Spectroscopy (²⁹Si NMR) ²⁹Si NMR data wascollected on a Varian Mercury 300 using chloroform D solvent. Theexperiment was conducted with a relaxation delay of 60 sec with a gateddecoupled pulse sequence using a 5 mm switchable PFG probe was used.Alternatively, the sample was run on a Mercury 400 using a Nalorac 16 mmsilicon free Pulsetune® probe with 0.03 M Cr(acac)₃ as a relaxationreagent and gated decoupling to ensure quantitative conditions. Bothused 90 degree pulsewidth and the 400 used a 12 sec relaxation delay.

SiH Measurement—The material was measured out (according to estimatedSiH content) in 125 mL Erlenmeyer flask to nearest 0.01 grams and sampleweight recorded. To this was added 20 mL of prepared mercuric acetatesolution (4% mercury acetate powder, 96% (1:1 mixture)methanol/chloroform), the flask was then covered and swirled to mix. Ablank sample (no SiH containing material added) was also prepared forcomparision. After samples stood for 30 minutes, they were quenched with20 mL of prepared calcium chloride solution (25% calcium chloride, 75%methanol). Then 10 drops of prepared phenolphthalein solution (1%phenolphthalein in ethanol) from small pipet was added. The samples werethen titrated with 0.1N methanolic potassium hydroxide and measurementstaken.

EXAMPLE 1

To a reaction vessel was added 2947 g of a poly(methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (49.1 molesSiH) and 5053 g of a dimethylvinylsiloxy end-blockedpolydimethylsiloxane polymer having an average Dp of about 8 (14.4 molesvinyl) to give an SiH/SiVi ratio of 3.4:1. The polymers were well mixedand a vinylsiloxane diluted platinum (Pt) catalyst added to give a Ptcontent of about 12 ppm. An exothermic reaction was initiated and over aperiod of 10 minutes the temperature of the vessel contents rose from25° C. to 137° C. After cooling for 2 hours,bis(2-methoxy-1-methylethyl)maleate (80 g, 1 wt %) was added tostabilize the Pt from further activity. The resulting polymer was notstripped and was shown by GC to have a remaining unreacted MeH cyclicscontent of about 4%. The isolated product had a viscosity of 78 mPa·s, aSiH level of 0.42 wt % (SiH as H) as determined by titration and a GPCMn=2810 and Mw=8115 vs polydimethylsiloxane (PDMS) standards. ²⁹Si NMRanalysis of the product demonstrated that all vinyl functionality hasbeen consumed yielding silethylene bridges, no ring opening has occurredand that the resulting molecular structure is consistent with amethylhydrogen cyclic siloxane capped linear siloxane polymer asdescribed below, where Me is methyl, x is an average of 6.5 for Mw andan average of 1.5 for Mn and d is an average of about 8.

EXAMPLE 2

To a reaction vessel was added 5211 g of a poly(methylhydrogen) cyclicsiloxane (MeH cyclics) having an average degree of polymerization (Dp)of about 4.4 (86.7 moles SiH) and 3340 g of a dimethylvinylsiloxyend-blocked polydimethylsiloxane having an average Dp of about 8 (9.6moles vinyl) to give an SiWSiVi ratio of 9:1. The polymers were wellmixed and a vinylsiloxane diluted platinum (Pt) catalyst added to give aPt content of about 12 ppm. An exothermic reaction was initiated andover a period of 10 minutes the temperature of the vessel contents rosefrom 23° C. to 100° C. After cooling for 30 minutes,bis(2-methoxy-1-methylethyl)maleate (60 g, 0.7 wt %) was added tostabilize the Pt from further activity. The resulting product wasstripped on a roto-vap at 1 mm Hg and 50° C. to remove unreactedpoly(methylhydrogen)cyclic siloxane. The isolated product had aviscosity of 23 mPa·s, a SiH level of 0.58 wt % (SiH as H) as determinedby titration and a GPC Mn=1396 and Mw=2753 vs PDMS standards. ²⁹Si NMRanalysis of the crosslinker product demonstrated that all vinylfunctionality has been consumed yielding silethylene bridges, no ringopening has occurred and that the resulting molecular structure isconsistent with a methylhydrogen cyclic siloxane capped linear siloxanepolymer, where Me is methyl, x is an average of 1.5 for Mw and averageof 0 for Mn, and d is an average of about 8.

EXAMPLE 3

To a reaction vessel was added 11.1 g of a poly(methylhydrogen)cyclosiloxane having an average Dp of about 4.4 and 50 g of adimethylvinylsiloxy end-blocked polydimethylsiloxane polymer having anaverage Dp of about 25 to give an SiH/SiVi ratio of 3.5:1. The polymerswere well mixed and a vinylsiloxane diluted Pt catalyst added to give aPt content of about 10 ppm. The typical and expected exothermic reactionwas observed. The resulting product was not stripped and was usedimmediately for performance evaluation without the Pt being deactivated.Titration showed that the product had an SiH level of 0.20 wt % (SiH asH). ²⁹Si NMR analysis of the product would demonstrate that all vinylfunctionality has been consumed yielding silethylene bridges, no ringopening has occurred and that the resulting molecular structure isconsistent with a methylhydrogen cyclic siloxane capped linear siloxanepolymer as described below, where Me is methyl, x is an average of 6.5for Mw and an average of 1.5 for Mn and d is an average of about 8.

EXAMPLE 4

To a reaction vessel was added 312 g of a poly(methylhydrogen)cyclosiloxane having an average Dp of about 4.4 (5.2 mol SiH) and 3000 gof a dimethylvinylsiloxy end-blocked polydimethylsiloxane polymer havingan average Dp of about 60 (1.5 mol Vi) to give an SiH/SiVi ratio of3.5:1. The polymers were well mixed and a vinylsiloxane diluted Ptcatalyst added to give a Pt content of about 10 ppm. The typical andexpected exothermic reaction was observed. After cooling for 3 hours,bis(2-methoxy-1-methylethyl)maleate (0.3% by weight, 9.9 g) was added todeactivate the Pt. The resulting polymer was isolated without strippingand gave a polymer of 1350 cP with a SiH content of 0.09 wt % (SiH asH). ²⁹Si NMR analysis of the product would demonstrate that all vinylfunctionality has been consumed yielding silethylene bridges, no ringopening has occurred and that the resulting molecular structure isconsistent with a methylhydrogen cyclic siloxane capped linear siloxanepolymer as described below, where Me is methyl, x is an average of 6.5for Mw and an average of 1.5 for Mn and d is an average of about 8.

EXAMPLE 5

To a reaction vessel was added 20.1 g of a poly(methylhydrogen)cyclosiloxane having an average Dp of about 4.4 (0.3 mol SiH) and 50 gof a dimethylvinylsiloxy end-blocked polydimethylsiloxane polymer havingan average Dp of about 60 (0.02 mol Vi) to give an SiH/SiVi ratio of15:1. The polymers were well mixed and a vinylsiloxane diluted Ptcatalyst added to give a Pt content of about 10 ppm. The typical andexpected exothermic reaction was observed. The resulting polymer wasstripped on a rotary evaporator to remove volatiles and was usedimmediately for performance evaluation without the Pt being deactivated.Titration showed that the product had an SiH level of 0.14 wt % (SiH asH). ²⁹Si NMR analysis of the product would demonstrate that all vinylfunctionality has been consumed yielding silethylene bridges, no ringopening has occurred and that the resulting molecular structure isconsistent with a methylhydrogen cyclic siloxane capped linear siloxanepolymer, where Me is methyl, x is an average of 1.5 for Mw and averageof 0 for Mn, and d is an average of about 8.

EXAMPLE 6

To a reaction vessel was added 297.1 g of a poly(methylhydrogen)cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (5.0 moles ofSiH) and 155.3 g of a vinyl endblocked polmer having an average Dp ofabout 25 (0.15 moles vinyl) to give a SiH/SiVi ratio of 33:1. Thepolymers were well mixed and a vinylsiloxane diluted Platinum (Pt)catalyst added to give a Pt content of about 12 ppm. The exothermicreaction resulted in a small to moderate temperature increase. Afterallowing the sample to cool for a few hours,bis(2-methoxy-1-methylethyl)maleate (0.4 g, 1 wt %.) was added tostabilize the Pt from further activity. The resulting polymer wasstripped on a rotovap at 1 mm Hg and 50 degrees Celsius to remove anyunreacted MeH cyclics. The isolated product had a viscosity of 49 mPa·s,a SiH level of 0.28 wt % (SiH as H) as determined by titration andmolecular weight as measured by GPC of Mn=2518 and Mw=33550 versuspolydimethylsiloxane (PDMS) standards. ²⁹ Si and ¹³C NMR analysis of theproduct demonstrated that all vinyl functionality has been consumedyielding silethylene bridges, no ring opening had occurred and that theresulting molecular structure is consistent with a methylhydrogen cyclicsiloxane capped linear siloxane polymer as described below, where Me ismethyl, x corresponds to 10 for Mw, 0 for Mn and d is an average ofabout 25.

EXAMPLE 7

To a reaction vessel was added 279.0 g of a poly(methylhydrogen)cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (4.7 moles ofSiH) and 175.0 g of 30 dp OH-endblocked polymer (0.16 mol OH) to give anSiH/SiOH ratio of 30:1. The polymers were well mixed and a vinylsiloxanediluted Platinum (Pt) catalyst added to give a Pt content of about 12ppm. The exothermic reaction resulted in a small to moderate temperatureincrease. After allowing the sample to cool for a few hours,bis(2-methoxy-1-methylethyl)maleate (0.40 g, 1 wt %) was added tostabilize the Pt from further activity. The resulting polymer wasstripped on a rotovap at 1 mm Hg and 50 degrees Celsius to remove anyunreacted poly(methylhydrogen)cyclic siloxane. The isolated product hada viscosity of 422 mPa·s, a SiH level of 0.22 wt % (SiH as H) asdetermined by titration and a molecular weight as determined by GPC ofMn=5510 and Mw=65260 vs. polydimethylsiloxane (PDMS) standards. ²⁹ Siand ¹³C NMR analysis of the product demonstrated that all OHfunctionality had been consumed yielding SiO_(3/2) structural units (T),no ring opening had occurred and that the resulting molecular structureis consistent with a methylhydrogen cyclic siloxane capped linearsiloxane polymer as described below, where Me is methyl, x is an averageof 18 for Mw, an average of 1.5 for Mn and d is an average of about 30.

EXAMPLE 8

To a reaction vessel was added 272.6 g of a poly(methylhydrogen)cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (4.5 moles ofSiH) and 175.0 g of a vinyldimethylsiloxy endblockedpoly(dimethylsiloxane-silicate) copolymer having an average dp of 100(0.093 mol vinyl) to give an SiH/SiVi ratio of 49:1. The polymers werewell mixed and a vinylsiloxane diluted Platinum (Pt) catalyst added togive a Pt content of about 12 ppm. The exothermic reaction resulted in asmall to moderate temperature increase. After allowing the sample tocool for a few hours, bis(2-methoxy-1-methylethyl)maleate (0.39 g, 1 wt%) was added to stabilize the Pt from further activity. The resultingpolymer was stripped on a rotovap at 1 mm Hg and 50 degrees Celsius toremove any unreacted MeH cyclics. The isolated product had a viscosityof 263 mPa·s, a SiH level of 0.15 wt % (SiH as H) as determined bytitration and a molecular weight as determined by GPC of Mn=5615 andMw=30030 vs. polydimethylsiloxane (PDMS) standards. ²⁹ Si and ¹³C NMRanalysis of the product demonstrates that all vinyl functionality hadbeen consumed yielding silethylene bridges, no ring opening had occurredand that the resulting nominal Mn molecular structure is consistent witha methylhydrogen cyclic siloxane capped siloxane polymer as describedbelow, where Me is methyl and d is about 25. Oligomers of this structurecan of course grow from any or all of the arms.

EXAMPLE 9

To a reaction vessel was added 238.2 g of a poly(methylhydrogen)cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (4.0 moles ofSiH) and 175.0 g of an endblocked and vinyl pendant polydimethylsiloxanecopolymer (0.08 mol vinyl) to give an SiH/SiVi ratio of 50:1. Thepolymers were well mixed and a vinylsiloxane diluted Platinum (Pt)catalyst added to give a Pt content of about 12 ppm. The exothermicreaction resulted in a small to moderate temperature increase. Afterallowing the sample to cool for a few hours,bis(2-methoxy-1-methylethyl)maleate (0.39 g, 1 wt %) was added tostabilize the Pt from further activity. The resulting polymer wasstripped on a rotovap at 1 mm Hg and 50 degrees Celsius to remove anyunreacted MeH cyclics. The isolated product had a viscosity of 295mPa·s, a SiH level of 0.15 wt % (SiH as H) as determined by titrationand a molecular weight as measured by GPC of Mn=6872 and Mw=21960 vs.polydimethylsiloxane (PDMS) standards. ²⁹Si and ¹³C NMR analysis of theproduct demonstrates that all vinyl functionality had been consumedyielding silethylene bridges, no ring opening had occurred and that theresulting nominal Mn molecular structure is consistent with amethylhydrogen cyclic siloxane capped pendant and endblocked PDMSsiloxane polymer as described below, where Me is methyl, d₁ is about 97and d₂ is about 1.3. Oligomers of this structure can grow from theendblocked or pendant arms.

EXAMPLE 10

To a reaction vessel was added 236.1 g of a poly(methylhydrogen)cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (3.9 moles ofSiH) and 175.0 g of an endblocked and hexenyl pendantpolydimethylsiloxane copolymer (0.076 mol vinyl) to give an SiH/SiViratio of 52:1. The polymers were well mixed and a vinylsiloxane dilutedPlatinum (Pt) catalyst added to give a Pt content of about 12 ppm. Theexothermic reaction resulted in a small to moderate temperatureincrease. After allowing the sample to cool for a few hours,bis(2-methoxy-1-methylethyl)maleate (0.39 g, 1 wt %) was added tostabilize the Pt from further activity. The resulting polymer wasstripped on a rotovap at 1 mm Hg and 50 degrees Celsius to remove anyunreacted poly(methylhydrogen)cyclic siloxane. The isolated product hada viscosity of 284 mPa·s, a SiH level of 0.17 wt % (SiH as H) asdetermined by titration and a molecular weight as determined by GPC ofMn=4282 and Mw=17290 vs. polydimethylsiloxane (PDMS) standards. ²⁹ Siand ¹³C NMR analysis of the product demonstrated that all vinylfunctionality had been consumed yielding silethylene bridges, no ringopening had occurred and that the resulting nominal Mn molecularstructure is consistent with a methylhydrogen cyclic siloxane cappedendblocked and pendant siloxane polymer as described below, where Me ismethyl, d₁ is about 97 and d₂ is about 1.3.

EXAMPLE 11

To a reaction vessel was added 289.7 g of a poly(methylhydrogen)cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (4.8 moles ofSiH) and 175.0 g of a trimethylsiloxy endblocked, vinyl pendantpolydimethylsiloxane copolymer having an average Dp of about 165 (0.089mol vinyl) to give an SiH/SiVi ratio of 54:1. The polymers were wellmixed and a vinylsiloxane diluted Platinum (Pt) catalyst added to give aPt content of about 12 ppm. The exothermic reaction resulted in a smallto moderate temperature increase. After allowing the sample to cool fora few hours, bis(2-methoxy-1-methylethyl)maleate (0.40 g, 1 wt %) wasadded to stabilize the Pt from further activity. The resulting polymerwas stripped on a rotovap at 1 mm Hg and 50 degrees Celsius to removeany unreacted poly(methylhydrogen)cyclics. The isolated product had aviscosity of 1020 mPa·s, a SiH level of 0.19 wt % (SiH as H) asdetermined by titration and a molecular weight as determined by GPC ofMn=8902 and Mw=60370 vs polydimethylsiloxane (PDMS) standards. ²⁹ Si and¹³C NMR analysis of the product demonstrates that all vinylfunctionality had been consumed yielding silethylene bridges, no ringopening had occurred and that the resulting nominal Mn molecularstructure is consistent with a methylhydrogen cyclic siloxane cappedvinyl pendant siloxane polymer as described below, where Me is methyl,d₁ is about 157 and d₂ is about 6.

EXAMPLE 12

To a reaction vessel was added 233.9 g of a poly(methylhydrogen)cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (3.9 moles ofSiH) and 175.0 g of a trimethylsiloxy endblocked, hexenyl pendantpolydimethylsiloxane copolymer (0.076 mol vinyl) to give an SiH/SiViratio of 51:1. The polymers were well mixed and a vinylsiloxane dilutedPlatinum (Pt) catalyst added to give a Pt content of about 12 ppm. Theexothermic reaction resulted in a small to moderate temperatureincrease. After allowing the sample to cool for a few hours,bis(2-methoxy-1-methylethyl)maleate (0.39 g, 1 wt %) was added tostabilize the Pt from further activity. The resulting polymer wasstripped on a rotovap at 1 mm Hg and 50 degrees Celsius to remove anyunreacted poly(methylhydrogen) cyclic. The isolated product had aviscosity of 585 mPa·s, a SiH level of 0.15 wt % (SiH as H) asdetermined by titration and a molecular weight as detemmined by GPC ofMn=7930 and Mw=50100 vs polydimethylsiloxane (PDMS) standards. ²⁹Si and¹³C NMR analysis of the product demonstrated that all vinylfunctionality had been consumed yielding silethylene bridges, no ringopening had occurred and that the resulting nominal Mn molecularstructure is consistent with a methylhydrogen cyclic siloxane cappedpendant siloxane polymer as described below, where Me is methyl, d₁ isabout 143 and d₂ is about 5.

EXAMPLE 13

To a reaction vessel was added 654.0 g of a poly(methylhydrogen)cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (6.9 moles ofSiH) and 110.0 g of a hexenyl endblocked polydimethylsiloxane polymer(0.25 mol vinyl) to give an SiH/SiVi ratio of 44:1. The polymers werewell mixed and a vinylsiloxane diluted Platinum (Pt) catalyst added togive a Pt content of about 12 ppm. The exothermic reaction resulted in asmall to moderate temperature increase. After allowing the sample tocool for a few hours, bis(2-methoxy-1-methylethyl)maleate (0.39 g, 1 wt%) was added to stabilize the Pt from further activity. The resultingpolymer was stripped on a rotovap at 1 mm Hg and 50 degrees Celsius toremove any unreacted poly(methylhydrogen)cyclic siloxane. The isolatedproduct had a viscosity of 29 mPa·s, a SiH level of 0.50 wt % (SiH as H)as determined by titration and a molecular weight as determined by GPCof Mn=1648 and Mw=16060 vs polydimethylsiloxane (PDMS) standards. ²⁹ Siand ¹³C NMR analysis of the product demonstrated that all vinylfunctionality has been consumed yielding silethylene bridges, no ringopenings had occurred and that the resulting molecular structure isconsistent with a methylhydrogen cyclic siloxane capped linear siloxanepolymer as described below, where Me is methyl, x corresponds to 8 forMw, 0 for Mn and d is an average of about 10.

EXAMPLE 14

To a reaction vessel was added 837.0 g of a poly(methylhydrogen)cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (14.0 moles ofSiH) and 65.0 g of tetrakis(vinyldimethylsiloxy)silane (0.60 mol vinyl)to give an SiH/SiVi ratio of 23:1. The polymers were well mixed and avinylsiloxane diluted Platinum (Pt) catalyst added to give a Pt contentof about 12 ppm. The exothermic reaction resulted in a small to moderatetemperature increase. After allowing the sample to cool for a few hours,bis(2-methoxy-1-methylethyl)maleate (0.40 g, wt %) was added tostabilize the Pt from further activity. The resulting polymer wasstripped on a rotovap at 1 mm Hg and 50 degrees Celsius to remove anyunreacted poly(methylhydrogen)cyclic siloxane. The isolated product hada viscosity of 81 mPa·s, a SiH level of 0.90 wt % (SiH as H) asdetermined by titration and a molecular weight as determined by GPC ofMn=1460 and Mw=18600 vs polydimethylsiloxane (PDMS) standards. ²⁹Si and¹³C NMR analysis of the product demonstrated that all vinylfunctionality has been consumed yielding silethylene bridges, no ringopening had occurred and that the resulting nominal molecular structurefor Mn is consistent with a methylhydrogen cyclic siloxane cappedsiloxane polymer as described below, where Me is methyl. Higheroligomers can grow from any of the branches.

EXAMPLE 15

To a reaction vessel was added 729.7 g of a poly(methylhydrogen)cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (12.2 moles ofSiH) and 85.0 g of tetrakis(hexenyldimethylsiloxy)silane (0.52 molvinyl) to give an SiH/SiVi ratio of 24:1. The polymers were well mixedand a vinylsiloxane diluted Platinum (Pt) catalyst added to give a Ptcontent of about 12 ppm. The exothermic reaction resulted in a small tomoderate temperature increase. After allowing the sample to cool for afew hours, bis(2-methoxy-1-methylethyl)maleate (0.40 g, wt %) was addedto stabilize the Pt from further activity. The resulting polymer wasstripped on a rotovap at 1 mm Hg and 50 degrees Celsius to remove anyunreacted poly(methylhydrogen)cyclic. The isolated product had aviscosity of 32 mPa·s, a SiH level of 0.70 wt % (SiH as H) as determinedby titration and a molecular weight as determined by GPC of Mn=1453 andMw=27690 vs polydimethylsiloxane (PDMS) standards. ²⁹Si and ¹³C NMRanalysis of the product demonstrated that all vinyl functionality hasbeen consumed yielding silethylene bridges, no ring opening had occurredand that the resulting nominal molecular structure for Mn is consistentwith a methylhydrogen cyclic siloxane capped siloxane polymer asdescribed below, where Me is methyl. Higher oligomers can grow from anyof the branches.

EXAMPLE 16

To a reaction vessel was added 381.1 g of a poly(methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (6.3 moles SiH)and 80.0 g of a dimethylvinylsiloxy end-blocked polydimethylsiloxanepolymer having an average Dp of about 7 (0.29 moles vinyl) to give anSiH/SiVi ratio of about 22:1. The polymers were well mixed and avinylsiloxane diluted platinum (Pt) catalyst was added to give a Ptcontent of 15 about 4 ppm. An exotherm reaction was initiated and over aperiod of 10 minutes the temperature of the vessel contents rose toabove room temperature. After cooling for 2 hours, the resulting polymerwas stripped in a rotovap at 1 mm Hg and 95 C to remove any unreactedpoly(methylhydrogen)cyclic siloxane. The material was then allowed tocool to room temperature. After cooling, 150 g of above product wasadded to another reaction vessel. Then 24.3 g (0.29 moles vinyl) of1-hexene was slowly added to the reaction vessel. An exothermic reactionwas initiated with each small addition. After cooling for 2 hours,bis(2-methoxy-1-methylethyl)maleate (0.87 g, 0.5 wt %) was added tostabilize the Pt from further activity. The resulting polymer was thenstripped a second time in a rotovap at 1 mm Hg and 95 C to remove anyunreacted 1-hexene. After cooling to room temperature,bis(2-methoxy-1-methylethyl)maleate (0.87 g, 0.5 wt %) was added tostabilize the Pt from further activity. The material was then allowed tocool to room temperature. The isolated product had a viscosity of 62mPa·s, a SiH level of 0.32% (SiH as H) as determined by titration and aGPC Mn=1723 and Mw=15640 versus polydimethylsiloxane (PDMS) standards.²⁹Si NMR analysis of the product demonstrates that all vinylfunctionality has been consumed yielding silethylene bridges, no ringopenings has occurred and that the resulting molecular structure isconsistent with a methylhydrogen cyclic siloxane capped linear siloxanepolymer as described below, where x is about 1 for Mn, about 9 for Mwand d is an average of about 7.

EXAMPLE 17

To a reaction vessel was added 737 g of a poly(methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (12.2 molesSiH) and 1263 g of a dimethylvinylsiloxy end-blockedpolydimethylsiloxane polymer having an average Dp of about 8 (3.6 molesvinyl) to give an SiH/SiVi ratio of 3.4:1. The polymers were well mixedand a vinylsiloxane diluted platinum (Pt) catalyst added to give a Ptcontent of about 4 ppm. An exothermic reaction was initiated and over aperiod of 10 minutes the temperature of the vessel contents rose from25° C. to 137° C. After the reaction mixture had cooled to 25 C, 91.1 g(0.80 mol) allylglycidylether (AGE) was added. The reaction was thenheated via heating mantle to 50 C at which point the heat was turnedoff. The reaction mixture continued to exotherm to 66 C over 5 minutesand held steady at 66 C for an additional 5 minutes. Analysis by gaschromatography at this point showed no trace of the AGE raw material.When the temperature began to drop, the heat was turned back on and thereaction mixture was maintained at 80 C for 2 hours. The reaction wasthen allowd to cool to 25 C. To stabilize the product, 4.2 g (0.2 wt. %)bis(2-methoxy-1-methylethyl)maleate was then added. The isolated producthad a viscosity of 93 mPa·s, a SiH level of 0.36% (SiH as H) asdetermined by titration and a GPC Mn=2626 and Mw=6405 versuspolydimethylsiloxane (PDMS) standards. The structure is shown below,where 10% of the SiH functions have been replaced with apropylglycidylether group, x=1-5 and d about 8.

EXAMPLE 18

To a reaction vessel was added 737.0 g of a poly(methylhydrogen) cyclicsiloxane (MeH cyclics) having an average Dp of about 4.4 (12.2 molesSiH) and 1263.0 g of a dimethylvinylsiloxy end-blockedpolydimethylsiloxane polymer having an average Dp of about 8 (3.6 molesvinyl) to give an SiH/SiVi ratio of 3.4:1. The polymers were well mixedand a vinylsiloxane diluted platinum (Pt) catalyst added to give a Ptcontent of about 4 ppm. An exothermic reaction was initiated and over aperiod of 10 minutes the temperature of the vessel contents rose from25° C. to 137° C. After the reaction mixture had cooled to 25 C, 227.9 g(2.0 mol) AGE was added. The reaction was then heated via heating mantleto 50 C at which point the heat was turned off. The reaction mixturecontinued to exotherm to 91 C over 10 minutes. Analysis by gaschromatography at this point showed no trace of the AGE raw material.When the reaction temperature had dropped back to 80 C, the heat wasturned back on and the reaction mixture was maintained at 80 C for 2hours. The reaction was then allowd to cool to 25 C. To stabilize theproduct, 4.2 g (0.2 wt. %) bis(2-methoxy-1-methylethyl)maleate was thenadded. The isolated product had a viscosity of 85 mPa·s, a SiH level of0.30% (SiH as H) as determined by titration and a GPC Mn=2867 andMw=7561 versus polydimethylsiloxane (PDMS) standards. The structure isshown below, where 25% of the SiH functions have been replaced with apropylglycidylether group, x=1-5 and d=about 8.

1. Organohydrogensilicon compounds containing at least onesilicon-bonded hydrogen atom per molecule described by formula (I)

where each R is independently selected from a hydrogen atom and amonovalent hydrocarbon group comprising 1 to 20 carbon atoms which isfree from aliphatic unsaturation, a is an integer from 1 to 18, b is aninteger from 1 to 19, a+b is an integer from 3 to 20, each X is anindependently selected functional group selected from a halogen atom, anether group, an alkoxy group, an alkoxyether group, an acyl group, anepoxy group, an amino group, or a silyl group, or a -Z-R⁴ group, whereeach Z is independently selected from an oxygen and a divalenthydrocarbon group comprising 2 to 20 carbon atoms, each R⁴ group isindependently selected from —BR_(u)Y_(2-u), —SiR_(v)Y_(3-v), or a groupdescribed by formula (II):(Y_(3-n)R_(n)SiO_(1/2))_(c)(Y_(2-o)R_(o)SiO_(2/2))_(d)(Y_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)Y_(1-q))_(g)(CR_(r)Y_(2-r))_(h)(O(CR_(s)Y_(2-s))_(i)(CR_(t)Y_(3-t))_(j)where B refers to boron, each R is as described above, the sum ofc+d+e+f+g+h+i+j is at least 2, n is an integer from 0 to 3, o is aninteger from 0 to 2, p is an integer from 0 to 1, q is an integer from 0to 1, r is an integer from 0 to 2, s is an integer from 0 to 2, t is aninteger from 0 to 3, u is an integer from 0 to 2, v is an integer from 0to 3, each Y is an independently selected functional group selected froma halogen atom, an ether group, an alkoxy group, an alkoxyether group,an acyl group, an epoxy group, an amino group, or a silyl group, or aZ-G group, where Z is as described above, each G is a cyclosiloxanedescribed by formula (III):

where R and X are as described above, k is an integer from 0 to 18, m isan integer from 0 to 18, k+m is an integer from 2 to 20, provided informula (II) that one of the Y groups is replaced by the Z group bondingthe R⁴ group to the cyclosiloxane of formula (I), and provided further(a) at least one X group of Formula (I) is a -Z-R⁴ group, (b) if Z is adivalent hydrocarbon group, a=1, c=2, e+f+g+h+i+j=0 and d>0, then atleast one d unit (ie. Y_(2-o)R_(o)SiO_(2/2)) contain a -Z-G group or thec units (ie. Y_(3-n)R_(n)SiO_(1/2)) have no -Z-G group or at least two-Z-G groups, (c) if Z is a divalent hydrocarbon group, a=1, c=2 andd+e+f+g+h+i+j=0, then the c units (ie. Y_(3-n)R_(n)SiO_(1/2)) have no-Z-G group or at least two -Z-G groups, and (d) if g+h+i+j>0 thenc+d+e+f>0.
 2. The organohydrogensilicon compounds of claim 1 wheresubscript b is an integer from 2 to 19, subscript c is an integer from 0to 50, subscript d is an integer from 0 to 5000, subscript e is aninteger from 0 to 48, subscript f is an integer from 0 to 24, subscriptg is an integer from 0 to 50, subscript h is an integer from 0 to 50,subscript i is an integer from 0 to 50, and subscript j is an integerfrom 0 to
 50. 3. The organohydrogen silicon compounds of claim 1 wheresubscript c is an integer from 2 to 15, subscript d is an integer from 0to 1000, subscript e is an integer from 0 to 13, subscript f is aninteger from 0 to 6, subscript g is an integer from 0 to 20, subscript his an integer from 0 to 20, subscript i is an integer from 0 to 20,subscript j is an integer from 0 to
 15. 4. The organohydrogensiliconcompounds of claim 1 where each R group is independently selected fromhydrogen atoms, alkyl groups comprising 1 to 8 carbon atoms, or arylgroups comprising 6 to 9 carbon atoms, each X is a Z-R⁴ group or isindependently selected from chloro, methoxy, isopropoxy, and groupsderived by are derived by hydrosilylation of the alkenyl group from fromhydroxybutylvinyl ether, vinylcyclohexylepoxide, and allylglycidyletherwith an SiH from the siloxane precursor to formulas (I) or (II), where Zis a divalent hydrocarbon group, and R⁴ is selected from—R₂SiO(R₂SiO)_(d)SiR₂-Z-G, —R₂SiOSiR₃, —R₂SiOSiR₂—Y, —RSi(OSiR₃)₂, whered is an integer from 1 to 50 and Z, G, and R are as described above. 5.The organohydrogensilicon compounds of claim 1 where each R group isindependently selected from hydrogen, methyl, alpha-methylstyryl,3,3,3-trifluoropropyl and nonafluorobutylethyl.
 6. Theorganohydrogensilicon compounds of claim 1 where R is methyl, and d isan average of
 8. 7. (canceled)
 8. The organohydrogensilicon compounds ofclaims 1 where such compounds are described by the structure below whereMe is methyl, d is an average of 8, and x is an integer from 1 to 15:


9. The organohydrogensilicon compounds of claim 26 where 5 to 70 percentof the SiH bonds are replaced by hydrocarbon, oxyhydrocarbon orfunctional groups.
 10. The organohydrogensilicon compounds of claims 26where 5 to 50 percent of the SiH bonds are replaced by functional groupsderived by hydrosilylation of allylglycidyl ether (propylglycidyl ethergroups) or vinylcyclohexylepoxide, alkyl groups or alkenyl groups. 11.The organohydrogensilicon compounds of claim 26 where 10 to 30 percentof the SiH bonds are replaced by functional groups derived byhydrosilylation of allylglycidyl ether (propylglycidyl ether groups).12. The organohydrogensilicon compounds of claim 1 where suchorganohydrogensilicon compounds contain at least 2 silicon-bondedhydrogen atoms per molecule.
 13. The organohydrogensilicon compounds ofclaim 1 where such organohydrogensilicon compounds contain at least 3silicon-bonded hydrogen atoms per molecule.
 14. Theorganohydrogensilicon compounds of claim 1 where such compounds have aviscosity from 5 to 50,000 mPa·s.
 15. A method of preparingorganohydrogensilicon compounds having at least one silicon-bondedhydrogen comprising (1) mixing (A) at least one organohydrogencyclosiloxane comprising at least 2 SiH bonds per molecule and havingthe formula

with (B) at least one compound comprising at least one aliphaticunsaturation or at least one hydroxy group per molecule described byBR_(u)A_(3-u), SiR_(v)A_(4-v), or a group described by formula(A_(3-n)R_(n)SiO_(1/2))_(c)(A_(2-o)R_(o)SiO_(2/2))_(d)(A_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)A_(1-q))_(g)(CR_(r)A_(2-r))_(h)(O(CR_(s)A_(2-s))_(i)(CR_(t)A_(3-t))_(j)so that the ratio of SiH bonds in component (A) to the aliphaticunsaturation or hydroxy group of component (B) is at least 2.5:1; (2)effecting a reaction between components (A) and (B) in the presence of(C) a catalyst to form a reaction mixture comprisingorganohydrogensilicon compounds having at least one SiH bond permolecule described by formula (I)

(3) optionally, adding an inhibitor to the reaction mixture; and (4)optionally, isolating the organohydrogen silicon compounds; where each Ris independently selected from a hydrogen atom and a monovalenthydrocarbon group comprising 1 to 20 carbon atoms which is free fromaliphatic unsaturation, a is an integer from 1 to 18, b is an integerfrom 1 to 19, a+b is an integer from 3 to 20, each X is an independentlyselected functional group selected from a halogen atom, an ether group,an alkoxy group, an alkoxyether group, an acyl group, an epoxy group, anamino group, or a silyl group, or a -Z-R⁴ group, where each Z isindependently selected from an oxygen and a divalent hydrocarbon groupcomprising 2 to 20 carbon atoms, each R⁴ group is independently selectedfrom —BR_(u)Y_(2-u), —SiR_(v)Y_(3-v), or a group described by formula(II):(Y_(3-n)R_(n)SiO_(1/2))_(c)(Y_(2-o)R_(o)SiO_(2/2))_(d)(Y_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)Y_(1-q))_(g)(CR_(r)Y_(2-r))_(h)(O(CR_(s)Y_(2-s))_(i)(CR_(t)Y_(3-t))_(i)where B refers to boron, each R is as described above, the sum ofc+d+e+f+g+h+i+j is at least 2, n is an integer from 0 to 3, o is aninteger from 0 to 2, p is an integer from 0 to 1, q is an integer from 0to 1, r is an integer from 0 to 2, s is an integer from 0 to 2, t is aninteger from 0 to 3, u is an integer from 0 to 2, v is an integer from 0to 3, each A is independently selected from a hydroxy group, amonovalent hydrocarbon group comprising 2 to about 20 carbon atomshaving at least one aliphatic unsaturation, a monovalent oxyhydrocarbongroup comprising 2 to about 20 carbon atoms having at least onealiphatic unsaturation, or a functional group selected from a halogenatom, an ether group, an alkoxy group, an alkoxyether group, an acylgroup, an epoxy group, an amino group, or a silyl group, provided atleast one A group has an aliphatic unsaturation or a hydroxy group, eachY is an independently selected functional group selected from a halogenatom, an ether group, an alkoxy group, an alkoxyether group, an acylgroup, an epoxy group, an amino group, or a silyl group, or a Z-G group,where Z is as described above, each G is a cyclosiloxane described byformula (III):

where R and X are as described above, k is an integer from 0 to 18, m isan integer from 0 to 18, k+m is an integer from 2 to 20, provided informula (II) that one of the Y groups is replaced by the Z group bondingthe R⁴ group to the cyclosiloxane of formula (I), and provided further(a) at least one X group of Formula (I) is a -Z-R⁴ group, (b) if Z is adivalent hydrocarbon group, a=1, c=2, e+f+g+h+i+j=0 and d>0, then atleast one d unit (ie. Y_(2-o)R_(o)SiO_(2/2)) contain a -Z-G group or thec units (ie. Y_(3-n)R_(n)SiO_(1/2)) have no -Z-G group or at least two-Z-G groups, (c) if Z is a divalent hydrocarbon group, a=1, c=2 andd+e+f+g+h+i+j=0, then the c units (ie. Y_(3-n)R_(n)SiO_(1/2)) have no-Z-G group or at least two -Z-G groups, and (d) if g+h+i+j>0 thenc+d+e+f>0.
 16. The method of claim 15 further comprising step (2a)adding at least one hydrocarbon, oxyhydrocarbon or functional compoundhaving at least one aliphatic unsaturation or hydroxy group to thereaction mixture comprising organohydrogensilicon compounds having atleast one SiH bond per molecule formed in step 2 so to form a secondreaction mixture comprising organohydrogensilicon compounds having atleast one SiH bond per molecule where 5 to 70% of the SiH bonds havebeen converted to a hydrocarbon, oxyhydrocarbon or functional group. 17.A method of preparing organohydrogensilicon compounds having at leastone silicon-bonded hydrogen comprising (1′) mixing (A) at least oneorganohydrogen cyclosiloxane comprising at least 2 SiH bonds permolecule and having the formula

with (C) a catalyst to form a SiH premix; (2′) effecting a reaction byadding to the SiH premix (B) at least one compound comprising at leastone aliphatic unsaturation or at least one hydroxy group per moleculedescribed by BR_(u)A_(3-u), SiR_(v)A_(4-v), or a group described byformula(A_(3-n)R_(n)SiO_(1/2))_(c)(A_(2-o)R_(o)SiO_(2/2))_(d)(A_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)A_(1-q))_(g)(CR_(r)A_(2-r))_(h)(O(CR_(s)A_(2-s))_(i)(CR_(t)A_(3-t))_(j)so that ratio of SiH bonds in component (A) to the aliphaticunsaturation or hydroxy group of component (B) is at least 2.5 to form areaction mixture comprising organohydrogensilicon compounds having atleast one SiH bond per molecule described by formula (I)

(3′) optionally, adding an inhibitor to the reaction mixture; and (4′)optionally, isolating the organohydrogensilicon compounds; where B isboron, each R is independently selected from a hydrogen atom and amonovalent hydrocarbon group comprising 1 to 20 carbon atoms which isfree from aliphatic unsaturation, a is an integer from 1 to 18, b is aninteger from 1 to 19, a+b is an integer from 3 to 20, each X is anindependently selected functional group selected from a halogen atom, anether group, an alkoxy group, an alkoxyether group, an acyl group, anepoxy group, an amino group, or a silyl group, or a -Z-R⁴ group, whereeach Z is independently selected from an oxygen and a divalenthydrocarbon group comprising 2 to 20 carbon atoms, each R⁴ group isindependently selected from —BR_(u)Y_(2-u), —SiR_(v)Y_(3-v), or a groupdescribed by formula (II):(Y_(3-n)R_(n)SiO_(1/2))_(c)(Y_(2-o)R_(o)SiO_(2/2))_(d)(Y_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)Y_(1-q))_(g)(CR_(r)Y_(2-r))_(h)(O(CR_(s)Y_(2-s))_(i)(CR_(t)Y_(3-t))_(j)where B refers to boron, each R is as described above, the sum ofc+d+e+f+g+h+i+j is at least 2, n is an integer from 0 to 3, o is aninteger from 0 to 2, p is an integer from 0 to 1, q is an integer from 0to 1, r is an integer from 0 to 2, s is an integer from 0 to 2, t is aninteger from 0 to 3, u is an integer from 0 to 2, v is an integer from 0to 3, each A is independently selected from a hydroxy group, amonovalent hydrocarbon group comprising 2 to about 20 carbon atomshaving at least one aliphatic unsaturation, a monovalent oxyhydrocarbongroup comprising 2 to about 20 carbon atoms having at least onealiphatic unsaturation, or a functional group selected from a halogenatom, an ether group, an alkoxy group, an alkoxyether group, an acylgroup, an epoxy group, an amino group, or a silyl group, provided atleast one A group has an aliphatic unsaturation or a hydroxy group, eachY is an independently selected functional group selected from a halogenatom, an ether group, an alkoxy group, an alkoxyether group, an acylgroup, an epoxy group, an amino group, or a silyl group, or a Z-G group,where Z is as described above, each G is a cyclosiloxane described byformula (III):

where R and X are as described above, k is an integer from 0 to 18, m isan integer from 0 to 18, k+m is an integer from 2 to 20, provided informula (II) that one of the Y groups is replaced by the Z group bondingthe R⁴ group to the cyclosiloxane of formula (I), and provided further(a) at least one X group of Formula (I) is a -Z-R⁴ group, (b) if Z is adivalent hydrocarbon group, a=1, c=2, e+f+g+h+i+j=0 and d>0, then atleast one d unit (ie. Y_(2-o)R_(o)SiO_(2/2)) contain a -Z-G group or thec units (ie. Y_(3-n)R_(n)SiO_(1/2)) have no -Z-G group or at least two-Z-G groups, (c) if Z is a divalent hydrocarbon group, a=1, c=2 andd+e+f+g+h+i+j=0, then the c units (ie. Y_(3-n)R_(n)SiO_(1/2)) have no-Z-G group or at least two -Z-G groups, and (d) if g+h+i+j>0 thenc+d+e+f>0.
 18. The method of claim 17 further comprising step (2′a)adding at least one hydrocarbon, oxyhydrocarbon or functional compoundhaving at least one aliphatic unsaturation or hydroxy group to thereaction mixture comprising organohydrogensilicon compounds having atleast one SiH bond per molecule formed in step 2′ so to form a secondreaction mixture comprising organohydrogensilicon compounds having atleast one SiH bond per molecule where 5 to 70% of the SiH bonds havebeen converted to a hydrocarbon, oxyhydrocarbon or functional group. 19.A method of preparing organohydrogensilicon compounds having at leastone silicon-bonded hydrogen comprising (1″) mixing (B) at least onecompound comprising at least one aliphatic unsaturation or at least onehydroxy group per molecule described by BR_(u)A_(3-u), SiR_(v)A_(4-v),or a group described by formula(A_(3-n)R_(n)SiO_(1/2))_(c)(A_(2-o)R_(o)Si_(2/2))_(d)(A_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)A_(1-q))_(g)(CR_(r)A_(2-r))_(h)(O(CR_(s)A_(2-s))_(i)(CR_(t)A_(3-t))_(j),with (C) a catalyst to form a aliphatic unsaturation premix or hydroxypremix respectively; (2″) effecting a reaction by adding the aliphaticunsaturation premix or hydroxy premix to (A) at least one organohydrogencyclosiloxane comprising at least 2 SiH bonds per molecule and havingthe formula

so that ratio of SiH bonds in component (A) to the aliphaticunsaturation or hydroxy group of component (B) is at least 2.5 to form areaction mixture comprising organohydrogensilicon compounds having atleast one SiH bond per molecule described by formula (I)

(3″) optionally, adding an inhibitor to the reaction mixture; and (4″)optionally, isolating the organohydrogensilicon compounds; where B isboron, each R is independently selected from a hydrogen atom and amonovalent hydrocarbon group comprising 1 to 20 carbon atoms which isfree from aliphatic unsaturation, a is an integer from 1 to 18, b is aninteger from 1 to 19, a+b is an integer from 3 to 20, each X is anindependently selected functional group selected from a halogen atom, anether group, an alkoxy group, an alkoxyether group, an acyl group, anepoxy group, an amino group, or a silyl group, or a -Z-R⁴ group, whereeach Z is independently selected from an oxygen and a divalenthydrocarbon group comprising 2 to 20 carbon atoms, each R⁴ group isindependently selected from —BR_(u)Y_(2-u), —SiR_(v)Y_(3-v), or a groupdescribed by formula (II):(Y_(3-n)R_(n)SiO_(1/2))_(c)(Y_(2-o)R_(o)SiO_(2/2))_(d)(Y_(1-p)R_(p)SiO_(3/2))_(e)(SiO_(4/2))_(f)(CR_(q)Y_(1-q))_(g)(CR_(r)Y_(2-r))_(h)(O(CR_(s)Y_(2-s))_(i)(CR_(t)Y_(3-t))_(j)where B refers to boron, each R is as described above, the sum ofc+d+e+f+g+h+i+j is at least 2, n is an integer from 0 to 3, o is aninteger from 0 to 2, p is an integer from 0 to 1, q is an integer from 0to 1, r is an integer from 0 to 2, s is an integer from 0 to 2, t is aninteger from 0 to 3, u is an integer from 0 to 2, v is an integer from 0to 3, each A is independently selected from a hydroxy group, amonovalent hydrocarbon group comprising 2 to about 20 carbon atomshaving at least one aliphatic unsaturation, a monovalent oxyhydrocarbongroup comprising 2 to about 20 carbon atoms having at least onealiphatic unsaturation, or a functional group selected from a halogenatom, an ether group, an alkoxy group, an alkoxyether group, an acylgroup, an epoxy group, an amino group, or a silyl group, provided atleast one A group has an aliphatic unsaturation or a hydroxy group, eachY is an independently selected functional group selected from a halogenatom, an ether group, an alkoxy group, an alkoxyether group, an acylgroup, an epoxy group, an amino group, or a silyl group, or a Z-G group,where Z is as described above, each G is a cyclosiloxane described byformula (III):

where R and X are as described above, k is an integer from 0 to 18, m isan integer from 0 to 18, k+m is an integer from 2 to 20, provided informula (II) that one of the Y groups is replaced by the Z group bondingthe R⁴ group to the cyclosiloxane of formula (I), and provided further(a) at least one X group of Formula (I) is a -Z-R⁴ group, (b) if Z is adivalent hydrocarbon group, a=1, c=2, e+f+g+h+i+j=0 and d>0, then atleast one d unit (ie. Y_(2-o)R_(o)SiO_(2/2)) contain a -Z-G group or thec units (ie. Y_(3-n)R_(n)SiO_(1/2)) have no -Z-G group or at least two-Z-G groups, (c) if Z is a divalent hydrocarbon group, a=1, c=2 andd+e+f+g+h+i+j=0, then the c units (ie. Y_(3-n)R_(n)SiO_(1/2)) have no-Z-G group or at least two -Z-G groups, and (d) if g+h+i+j>0 thenc+d+e+f>0.
 20. The method of claim 19 further comprising step (2″a)adding at least one hydrocarbon, oxyhydrocarbon or functional compoundhaving at least one aliphatic unsaturation or hydroxy group to thereaction mixture comprising organohydrogensilicon compounds having atleast one SiH bond per molecule formed in step 2″ so to form a secondreaction mixture comprising organohydrogensilicon compounds having atleast one SiH bond per molecule where 5 to 70% of the SiH bonds havebeen converted to a hydrocarbon, oxyhydrocarbon or functional group. 21.The method of claim 16 where the hydrocarbon, oxyhydrocarbon orfunctional compound having at least one aliphatic unsaturation orhydroxy group is allylglycidylether.
 22. The method of claim 12 wheresubscript b is 2 to
 19. 23. The method of claim 18 where thehydrocarbon, oxyhydrocarbon or functional compound having at least onealiphatic unsaturation or hydroxy group is allylglycidylether.
 24. Themethod of claim 20 where the hydrocarbon, oxyhydrocarbon or functionalcompound having at least one aliphatic unsaturation or hydroxy group isallylglycidylether.
 25. The organohydrogensilicon compounds of claim 8where 10 to 30 percent of the SiH bonds are replaced by functionalgroups derived by hydrosilylation of allylglycidyl ether (propylglycidylether groups).
 26. The organohydrogensilicon compounds of claim 1 wheresuch compounds are selected from the structures below where Me ismethyl, d¹+d²=d, and x can range from 1 to 100: